The surface adsorption characteristics of red spruce (Picea rubens) roots were examined as a function of changes in external acidity and cation concentrations. Root cation exchange capacity varied significantly with changes in pH, increasing from 110 micromol(c) g(-1) at pH 3.5 to 155 micromol(c) g(-1) at pH 4.5, and reaching 250 micromol(c) g(-1) at pH 7.0. In general, Al adsorption by spruce roots was much greater than either Ca or Mg adsorption under the same initial conditions. However, root affinity for the divalent cations was proportionately much more sensitive to pH changes than was root affinity for Al. The fractions of adsorbed Ca and Mg increased by 50 to 100% as pH increased from 3.5 to 4.5, whereas the fraction of adsorbed Al remained relatively constant at both initial pH conditions. Competition experiments at pH 3.5 and 4.5 indicated that Al adsorption was strongly favored over Ca adsorption, except at low Al concentrations (~10 micromol l(-1)), high solution Ca(2+)/Al(3+) ion activity ratios (> 1.5 to 5.0), and at the higher pH. These results suggest that cell wall exchange sites in red spruce roots will tend to become progressively saturated with Al under the prevailing conditions of many acidic forest soils. To the extent that root adsorbed Al interferes with the active uptake of Ca and Mg, this process of competitive cation adsorption can contribute to impaired mineral nutrition in the spruce forest community.